Technical Field
[0001] The present invention relates to a high modulus multilayer oriented film with a first
outer layer comprising a polyester or co-polyester, a second outer layer comprising
an ethylene- or propylene- homo- or co-polymer, a core layer comprising an ethylene-vinyl
alcohol copolymer, and no polyamide or polyester core layers.
[0002] The invention also relates to a process for the manufacture of the new film and to
the use of the new film in packaging applications.
Background Art
[0003] Oriented films with a first outer layer of a polyester or copolyester, a second outer
layer of a polyolefin, and a gas-barrier layer of EVOH have been described in the
patent literature, see for instance
EP-A-476,836,
WO 99/55528,
WO 99/44824,
WO 99/44823,
EP-A-1,190,847, and
WO 01/98081.
[0004] In all those cases, the structures containing a first outer polyester layer, a second
outer polyolefin layer, and a core EVOH layer also contain a core polyamide or polyester
layer.
[0005] In particular,
EP-A-476,836 describes an oriented laminated film with a surface layer of a polyester, an EVOH
core layer, an intermediate layer of certain polyamides and a heat-sealing layer of
polyolefin. In the structures there claimed a given thickness ratio between the outer
polyester layer and the core polyamide layer needs to be present, what improves orientability
of the tape. The films described there are said to have excellent stretching processability,
heat-sealing and packaging properties and good transparency after heat-sterilization.
[0006] WO 99/44824 and
WO 99/44823 describe EVOH-containing heat-shrinkable films with at least four layers, i.e. a
first outer layer comprising i.a. a polyethylene, a second outer layer possibly comprising
a polyester, a core EVOH layer and an additional core polyamide or polyester layer.
The bags obtained therefrom can be stacked on top of one another and sealed simultaneously
and the presence of the core polyamide or polyester layer is said to give i.a. enhanced
impact strength and render the tape more easily orientable.
[0007] WO 99/55528,
EP-A-1,190,847, and
WO 01/98081 relate to heat-shrinkable structures where in addition to the polyester and polyolefin
outer layers, a core polyamide layer is always present and optionally also an EVOH
core layer. These films are said to satisfy various properties required of a packaging
material, through e.g. a control of the heat-shrinkage stress and of the heat-shrink.
[0008] In all the above documents the process actually described for the manufacture of
these films is the so-called trapped bubble process. According to this technique,
the polymer feeds are extruded through an annular die to give a thick tubing, called
"tape". Said tubing is quickly quenched at the exit of the extrusion die in order
to control crystallization, then it is re-heated to the suitably selected orientation
temperature and oriented transversely by inflating it with a gas to expand its diameter
and longitudinally by running the nip rolls that hold the bubble at a differential
speed.
[0009] It has now been found that it is possible to obtain biaxially oriented films with
a first outer layer of a polyester or copolyester, a second outer layer comprising
an ethylene- or propylene- homo- or co-polymer, and a core layer comprising EVOH,
without needing any polyamide or polyester core layer, by carrying out the biaxial
orientation of the extruded tape simultaneously by means of a tenter frame.
[0010] It has been found that the films which are thus obtained have a high modulus in at
least one direction, and are therefore very useful for most of the currently used
packaging systems as it is known that for a good machinability, as well as for a good
printability, the packaging material needs to be stiff, i.e. it should have a high
modulus.
[0011] The films of the present invention are in particular characterized by a modulus which
is higher than 6,000 kg/cm
2 in at least one direction.
[0012] Preferred films according to the present invention have a modulus which is higher
than 6,500 kg/cm
2 in at least one direction, and more preferred are those films which have a modulus
higher than 7,000 kg/cm
2 in at least one direction.
[0013] It has also been found that when a heat-shrinkable structure is obtained, it is possible
to conjugate a high free shrink with a low shrink force, particularly in the transverse
direction. This would be an advantage in all the packaging applications where the
product to be packaged is sensitive to a high shrink force and in particular can be
crushed or distorted by films with a high shrink force when these films are shrunk
around the product.
[0014] Preferred heat-shrinkable films according to the present invention have in fact a
free shrink of at least 10 % in each direction at 120 °C and a maximum shrink tension
in the transverse direction, in the temperature range of from 20 to 180 °C of less
than 5 kg/cm
2, more preferably less than 3 kg/cm
2, and even more preferably less than 1 kg/cm
2.
Disclosure of Invention
[0015] A first object of the present invention is therefore a multi-layer, bi-axially oriented,
thermoplastic film comprising a first outer layer comprising a polyester or a copolyester,
a second outer layer comprising an ethylene- or propylene- homo- or copolymer, a core
layer comprising an ethylene-vinyl alcohol copolymer, and no core polyamide or polyester
layers, said film having a modulus (evaluated according to ASTM D882) higher than
6,000 kg/cm
2, preferably higher than 6,500 kg/cm
2, and more preferably higher than 7,000 kg/cm
2, in at least one direction.
[0016] In one embodiment the multi-layer, biaxially oriented, thermoplastic film of the
present invention is heat-shrinkable and has a free shrink of at least 10 % in each
direction at 120 °C and a maximum shrink tension, in the transverse direction, in
the temperature range of from 20 to 180 °C of less than 5 kg/cm
2, more preferably less than 3 kg/cm
2, and even more preferably less than 1 kg/cm
2.
[0017] In another embodiment the multi-layer bi-axially oriented thermoplastic film of the
present invention is a non-shrinkable, heat-set, film with a free shrink at 120 °C
which is ≤ 10%, preferably ≤ 5%, more preferably ≤ 3% in each direction.
[0018] A second object is the process for the manufacture of a film of the first object
by co-extrusion of a tape through a flat die followed by bi-axial orientation, with
an orientation ratio generally comprised between 2:1 and 5:1 in each direction, by
means of a tenter frame, said orientation step being optionally followed by a heat-setting
step.
[0019] The biaxial orientation is carried out simultaneously in both directions, by a simultaneous
tenter frame.
[0020] A third object of the present invention is the use of a film according to the first
object in packaging applications.
Mode for the Invention
DEFINITIONS
[0021] As used herein, the term "film" is used in a generic sense to include plastic web,
regardless of whether it is film or sheet. Typically, films of and used in the present
invention have a thickness of 150 µm or less, preferably they have a thickness of
120 µm or less, more preferably a thickness of 100 µm or less, still more preferably
a thickness of 75 µm or less, and yet, still more preferably, a thickness of 60 µm
or less.
[0022] As used herein, the phrase "outer layer" refers to any layer of film having only
one of its principal surfaces directly adhered to another layer of the film.
[0023] As used herein, the phrases "inner layer" and "internal layer" refer to any layer
having both of its principal surfaces directly adhered to another layer of the film.
[0024] As used herein, the phrase "inside layer" when referred to a package made using the
multi-layer film of the invention refers to the outer layer of the film which is closest
to the packaged product, relative to the other layers thereof.
[0025] As used herein, the phrase "outside layer" when referred to a package made using
the multi-layer film of the invention refers to the outer layer of the film which
is furthest from the product relative to the other layers thereof.
[0026] As used herein, the term "core", and the phrase "core layer", refers to any internal
layer that preferably has a function other than serving as an adhesive or compatibilizer
for adhering two layers to one another.
[0027] As used herein, the phrases "seal layer", "sealing layer", "heat seal layer", and
"sealant layer", refer to an outer layer involved in the sealing of the film to itself,
to another layer of the same or another film, and/or to another article which is not
a film. With respect to packages having only fin-type seals, as opposed to lap-type
seals, the phrase "sealant layer" generally refers to the inside layer of a package.
[0028] As used herein, the phrase "tie layer" refers to any internal layer having the primary
purpose of adhering two layers to one another. Preferred polymers for use in tie layers
include, but are not restricted to, suitably modified polyolefins and blends thereof
with polyolefins.
[0029] As used herein, the phrase "machine direction", herein abbreviated "MD", refers to
a direction "along the length" of the film, i.e., in the direction of the film as
the film is formed during extrusion and/or coating.
[0030] As used herein, the phrase "transverse direction", herein abbreviated "TD", refers
to a direction across the film, perpendicular to the machine or longitudinal direction.
[0031] As used herein, the phrases "orientation ratio" and "stretching ratio" refer to the
multiplication product of the extent to which the plastic film material is expanded
in the two directions perpendicular to one another, i.e. the machine direction and
the transverse direction.
[0032] As used herein, the phrases "heat-shrinkable," "heat-shrink," and the like, refer
to the tendency of the film to shrink upon the application of heat, i.e., to contract
upon being heated, such that the size of the film decreases while the film is in an
unrestrained state. As used herein said term refer to films with a free shrink in
at least one direction, as measured by ASTM D 2732, of at least 10 % at 120 °C.
[0033] As used herein, the term "polymer" refers to the product of a polymerization reaction,
and is inclusive of homo-polymers, and co-polymers.
[0034] As used herein, the term "homo-polymer" is used with reference to a polymer resulting
from the polymerization of a single monomer, i.e., a polymer consisting essentially
of a single type of mer, i.e., repeating unit.
[0035] As used herein, the term "co-polymer" refers to polymers formed by the polymerization
reaction of at least two different monomers. The term "co-polymer" is also inclusive
of random co-polymers, block co-polymers, and graft co-polymers.
[0036] As used herein, the phrase "heterogeneous polymer" refers to polymerization reaction
products of relatively wide variation in molecular weight and relatively wide variation
in composition distribution, i.e., typical polymers prepared, for example, using conventional
Ziegler-Natta catalysts. Although there are a few exceptions (such as TAFMER™ linear
homogeneous ethylene-α-olefin copolymers produced by Mitsui, using Ziegler-Natta catalysts),
heterogeneous polymers typically contain a relatively wide variety of chain lengths
and co-monomer percentages.
[0037] As used herein, the phrase "homogeneous polymer" refers to polymerization reaction
products of relatively narrow molecular weight distribution and relatively narrow
composition distribution. Homogeneous polymers are structurally different from heterogeneous
polymers, in that homogeneous polymers exhibit a relatively even sequencing of co-monomers
within a chain, a mirroring of sequence distribution in all chains, and a similarity
of length of all chains, i.e., a narrower molecular weight distribution. Furthermore,
homogeneous polymers are typically prepared using metallocene, or other single-site
type catalysts, rather than using Ziegler Natta catalysts.
[0038] As used herein, the term "polyolefin" refers to the polymer or co-polymer resulting
from the polymerisation or co-polymerisation of unsaturated aliphatic, linear or cyclic,
straight or branched, hydrocarbon monomers that may be substituted or unsubstituted.
More specifically, included in the term polyolefin are film-forming homo-polymers
of olefin, co-polymers of olefin, co-polymers of an olefin and an non-olefinic co-monomer
co-polymerizable with the olefin, e.g. vinyl monomers. Specific examples include polyethylene
homo-polymer, polypropylene homo-polymer, polybutene homo-polymer, ethylene-α-olefin
co-polymer, propylene-α-olefin copolymer, butene-α-olefin co-polymer, ethylene-unsaturated
ester co-polymer, ethylene-unsaturated acid co-polymer, (e.g., ethylene-(C
1-C
4)alkyl acrylate or methacrylate copolymers, such as for instance ethylene-ethyl acrylate
co-polymer, ethylene-butyl acrylate co-polymer, ethylene-methyl acrylate co-polymer,
ethylene-methyl methacrylate co-polymer, ethylene-acrylic acid co-polymer, and ethylene-methacrylic
acid co-polymer), ionomer resin, polymethylpentene, etc.
[0039] As used herein the term "modified polyolefin" is inclusive of modified polymers prepared
by co-polymerizing the homo-polymer of the olefin or co-polymer thereof with an unsaturated
carboxylic acid, e.g., maleic acid, fumaric acid or the like, or a derivative thereof
such as the anhydride, ester or metal salt. It is also inclusive of modified polymers
obtained by incorporating into the olefin homo-polymer or co-polymer, by blending
or preferably by grafting, an unsaturated carboxylic acid, e.g., maleic acid, fumaric
acid or the like, or a derivative thereof such as the anhydride, ester or metal salt.
[0040] As used herein, the phrase " ethylene-α-olefin copolymer" refer to such heterogeneous
materials as linear low density polyethylene (LLDPE, with a density usually in the
range of from 0.915 g/cm
3 to 0.930 g/cm
3), linear medium density polyethylene (LMDPE, with a density usually in the range
of from 0.930 g/cm
3 to 0.945 g/cm
3) and very low and ultra low density polyethylene (VLDPE and ULDPE, with a density
usually lower than 0.915 g/cm
3); and homogeneous polymers such as metallocene-catalyzed homogeneous ethylene-α-olefin
copolymer resins and linear homogeneous ethylene-α-olefin copolymer resins obtainable
under homogeneous catalysis conditions but using Ziegler-Natta catalysts (Tafmer®
resins by Mitsui). All these materials generally include co-polymers of ethylene with
one or more co-monomers selected from C
4 to C
10 α-olefin such as butene-1, hexene-1, octene-1, in which the molecules of the copolymers
comprise long chains with relatively few side chain branches or cross-linked structures.
[0041] As used herein, the term "adhered", as applied to film layers, broadly refers to
the adhesion of a first layer to a second layer either with or without an adhesive,
a tie layer or any other layer therebetween, and the word "between", as applied to
a layer expressed as being between two other specified layers, includes both direct
adherence of the subject layer to the two other layers it is between, as well as a
lack of direct adherence to either or both of the two other layers the subject layer
is between, i.e., one or more additional layers can be imposed between the subject
layer and one or more of the layers the subject layer is between.
[0042] In contrast, as used herein, the phrase "directly adhered" is defined as adhesion
of the subject layer to the object layer, without a tie layer, adhesive, or other
layer therebetween.
[0043] As used herein, "EVOH" refers to ethylene/vinyl alcohol copolymer. EVOH includes
saponified or hydrolyzed ethylene/vinyl acetate copolymers, and refers to a vinyl
alcohol copolymer having an ethylene comonomer, and prepared by, for example, hydrolysis
of vinyl acetate copolymers. The degree of hydrolysis is preferably at least 50%,
and more preferably, at least 85%. Preferably, the EVOH comprises from 28 to 48 mole
% ethylene, more preferably, from 32 to 44 mole % ethylene.
[0044] As used herein, the term "polyamide" refers to both polyamide homo-polymers and polyamide
co-polymers, also called co-polyamides.
[0045] As used herein the term "co-polyamide" on the other hand identifies the polyamide
product built from at least two different starting materials, i.e. lactams, aminocarboxylic
acids, equimolar amounts of diamines and dicarboxylic acids, in any proportion; this
term therefore also encompasses ter-polyamides and, in general, multi-polyamides.
[0046] As used herein the terms "major proportion" and "minor proportion" when referred
to a resin as a component of a layer, refer to an amount respectively higher than
50 wt. % or lower than 50 wt. % of said resin calculated on the overall weight of
the layer.
[0047] As used herein with the terms "polyamide layer" or "polyester layer" it is intended
to refer to layers comprising a major proportion of polyamide or of polyester respectively.
DETAILED DESCRIPTION OF THE INVENTION
[0048] In the film according to the present invention, the first outer layer, that in the
use of the film in packaging applications will be the outside, abuse-resistant, optionally
printed layer, comprises a film forming polyester or co-polyester. Suitable film forming
polyesters and co-polyesters can be crystalline, semi-crystalline, or amorphous. If
crystalline or semi-crystalline, their melting point is preferably comprised between
100°C and 260°C, and is higher, preferably at least 10°C higher, and even more preferably
at least 20°C higher, than the melting point of the polyolefin resin of the second
outer layer, in order to favor heat-sealability of the film through said second outer
layer. The Tg of the film forming polyesters or copolyesters used for the first outer
layer needs to be below 130°C, in order to allow orientation of the extruded structure
at conventional temperatures. Preferably said Tg will be below 110°C, more preferably
below 100°C, and even more preferably below 90°C.
[0049] Preferred polyesters and co-polyesters are aromatic ring-containing polymers.
[0050] Suitable linear homopolymeric polyesters include e.g. poly(ethylene terephthalate),
poly(1,2-propylene terephthalate), poly(ethylene 2,5-dimethyl-terephthalate), poly(butylene
terephthalate), poly(ethylene isophthalate), poly(ethylene 5-t-butyl-isophthalate),
and poly(butylene 2,6-naphthalate).
[0051] Suitable copolymers can be random copolymers, i.e. those copolymers where the various
components are randomly incorporated into the copolymer chain; alternating or patterned
copolymers, i.e. those copolymers whose constituent units stand in a regular pattern
of succession along the molecular chains; or block or segmented copolymers.
[0052] Examples of dicarboxylic acids that can be included in the copolyester resin are
terephthalic acid, isophthalic acid, 2,5-dimethyl-terephthalic acid, 5-t-butyl-isophthalic
acid, naphthalene dicarboxylic acid, cyclohexane-dicarboxylic acid, diphenyl ether
dicarboxylic acid, sebacic acid, adipic acid and azelaic acid. Examples of diols that
can be included in the copolyester resins are ethylene glycol, 1,2-propane-diol, 1,3-propane-diol,
1,4-butanediol, 1,6-hexane-diol, 1,4-cyclohexane-dimethanol, and 2,2-bis(4-hydroxyphenyl)propane.
[0053] In the copolyester at least one of the carboxylic acids or of the diols is used in
combination of at least two species.
[0054] The first outer layer may also comprise a blend of at least two components independently
selected from polyesters and copolyesters.
[0055] Said layer may also comprise minor proportions of other compatible polymers and/or
copolymers blended therein, such as polyamides and copolyamides, polyurethanes, and
the like polymers.
[0056] Preferably however said first outer layer will comprise at least 70 wt. %, more preferably
at least 80 wt. %, and even more preferably at least 90 wt. % calculated on the basis
of the overall weight of the layer, of one or more polyesters and/or one or more copolyesters.
[0057] In a most preferred embodiment said first outer layer will be essentially made of
one or more polyesters and/or one or more copolyesters.
[0058] Said first outer layer may also contain nucleating agents as known in the art (see
for instance Table 1 of the Literature Review by H. Zhou available at the internet
address
www.crd.ge.com as 98CRD138). A class of particularly preferred nucleating agents are the inorganic
compounds such as talc, silicate, clay, titanium dioxide, and the like. These compounds
can be used in an amount of less than 5 % by weight, typically in an amount of 1-2
% by weight on the total weight of the layer. Other preferred nucleating agents are
certain compatible polymers such as fluoropolymers (PTFE) and the faster crystallising
polymers that can be blended with the polyester and/or copolyester of the first outer
layer in an amount of up to e.g. 5-10 % by weight.
[0059] The thickness of said first outer layer will typically be up to 45 % of the thickness
of the overall structure, preferably up to 40 %, more preferably up to 35 % of the
overall thickness.
[0060] Typically the thickness of said first outer layer will be comprised between 8 and
40 %, and preferably between 10 and 35 %, of the overall film thickness.
[0061] The second outer layer, that in the end package will be the inside, preferably heat-sealable,
layer, will comprise one or more polymers selected from the group of ethylene homopolymers,
ethylene co-polymers, propylene homopolymers and propylene co-polymers.
[0062] Ethylene homo- and co-polymers suitable for the second outer layer are selected from
the group consisting of ethylene homo-polymers (polyethylene), heterogeneous or homogeneous
ethylene-α-olefin copolymers, ethylene-vinyl acetate co-polymers, ethylene-(C
1-C
4) alkyl acrylate or methacrylate co-polymers, such as ethylene-ethyl acrylate co-polymers,
ethylene-butyl acrylate co-polymers, ethylene-methyl acrylate co-polymers, and ethylene-methyl
methacrylate co-polymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid
co-polymers, and blends thereof in any proportion.
[0063] Preferred ethylene homo- and co-polymers for said second outer layer are e.g. polyethylene
having a density of from 0.900 g/cm
3 to 0.950 g/cm
3, heterogeneous and homogeneous ethylene-α-olefin copolymers having a density of from
0.880 g/cm
3 to 0.945 g/cm
3, more preferably of from 0.885 g/cm
3 to 0.940 g/cm
3, yet more preferably of from 0.890 g/cm
3 to 0.935 g/cm
3 , and ethylene-vinyl acetate copolymers comprising from 3 to 28 %, preferably, from
4 to 20 %, more preferably, from 4.5 to 18 % vinyl acetate comonomer, and blends thereof.
[0064] Even more preferred ethylene homo- and co-polymers for said second outer layer are
selected from the group consisting of heterogeneous ethylene-α-olefin copolymers having
a density of from 0.890 g/cm
3 to 0.940 g/cm
3, homogeneous ethylene-α-olefin copolymers having a density of from 0.890 g/cm
3 to 0.925 g/cm
3, ethylene-vinyl acetate copolymers comprising from 4.5 to 18 % vinyl acetate comonomer,
and blends thereof.
[0065] In one embodiment of the present invention the second outer layer comprises a blend
of at least two different ethylene-α-olefin copolymers with a density of from 0.890
g/cm
3 to 0.935 g/cm
3, more preferably a blend of a homogeneous and a heterogeneous ethylene-α-olefin copolymer,
optionally blended with ethylenevinyl acetate copolymer.
[0066] Preferably, the ethylene homo- or co-polymers for said second outer layer have a
melt index of from 0.3 to 10 g/10 min, more preferably from 0.5 to 8 g/10 min, still
more preferably from 0.8 to 7 g/10 min, even more preferably from 1 to 6 g/10 min
(as measured by ASTM D1238 -190 °C, 2.16 kg).
[0067] Propylene homo- and co-polymers suitable for the second outer layer are selected
from the group consisting of propylene homo-polymers (polypropylene), crystalline
or highly amorphous (i.e., a polypropylene with a crystalline fraction of not more
than 10 wt. %), and propylene copolymers with up to 50 wt.%, preferably up to 35 wt.%,
of ethylene and/or a (C
4 -C
10)-α-olefin, and blends thereof in any proportion.
[0068] Preferred propylene homo- and co-polymers for said second outer layer are e.g. polypropylene,
and propylene copolymers with up to 35 wt.%, of ethylene and/or butene-1, pentene-1,
or hexene-1, and blends thereof in any proportion.
[0069] Even more preferred propylene homo- and co-polymers for said second outer layer are
selected from the group consisting of highly amorphous polypropylene, propylene-ethylene
copolymers with an ethylene content lower than 25 wt.%, more preferably lower than
15 wt.% and even more preferably lower than 12 wt.%, propylene-ethylene-butene co-polymers
and propylene-butene-ethylene copolymers with a total ethylene and butene content
lower than 40 wt.%, preferably lower than 30 wt.%, and even more preferably lower
than 20 wt. %.
[0070] Preferably, the propylene homo- or co-polymers for said second outer layer have a
melt index of from 0.5 to 20 g/10 min, more preferably from 0.8 to 12 g/10 min, still
more preferably from 1 to 10 g/10 min (as measured by ASTM D1238 - 230°C, 2.16 kg).
[0071] Said second outer layer may also contain a blend of one or more ethylene homo-and/or
co-polymers with one or more propylene homo- and/or co-polymers, in any proportion.
[0072] Preferably however said second outer layer will comprise an ethylene homo- or copolymer.
[0073] The second outer layer may also comprise a blend of a major proportion of one or
more polymers of the group of ethylene homo- and copolymers and propylene homoand
copolymers, with a minor proportion of one or more other polyolefins or modified polyolefins,
such as polybutene homo-polymers, butene-(C
5 -C
10)-α-olefin copolymers, ionomers, anhydride grafted ethylene-α-olefin copolymers, anhydride
grafted ethylenevinyl acetate copolymers, anhydride grafted propylene homopolymer,
anhydride grafted propylene copolymer, or rubber modified ethylene-vinyl acetate copolymers
[0074] Said additional polymers may be blended with the basic polymers of said second outer
layer in an amount that is typically up to 40 % by weight, preferably up to 30 % by
weight, more preferably up to 20 % by weight, and still more preferably up to 10 %
by weight.
[0075] In a preferred embodiment however said second outer layer will essentially consist
of one or more polymers selected from the group of ethylene homo- and co-polymers,
and propylene homo- and co-polymers.
[0076] The thickness of said second outer layer may vary widely depending on the overall
structure of the end film. More particularly it can range from 1-2 µm up to 60 % or
more of the overall thickness of the film. Generally it is at least 5 % of the overall
thickness of the structure, being typically comprised between 5 and 60 % of the overall
thickness of the film.
[0077] The film according to the present invention also contains a core layer, which acts
as a gas-barrier layer, comprising an ethylene-vinyl alcohol copolymer.
[0078] The gas-barrier layer - as indicated - may comprise one or more EVOH optionally admixed
with a minor amount of one or more polyamide components, as known in the art. In particular
said core layer will comprise at least 70 %, still more preferably at least 80 %,
and yet still more preferably at least 90 % by weight of a single EVOH or a blend
of two or more EVOHs. Examples of EVOH that may well be employed in the production
of films according to the present invention are EVAL™ EC F151A or EVAL™ EC F101A,
marketed by Marubeni. The possible complement to 100 % in said core gas-barrier layer
is typically made of one or more polyamides, either aliphatic or aromatic, e.g. such
as those commonly indicated as nylon 6, nylon 66, nylon 6/66, nylon 12, nylon 6,12,
nylon 6I/6T, and nylon MXD6/MXDI. In such a case a preferred polyamide is nylon 6/12,
a copolymer of caprolactam with laurolactam, such as GRILON™ CF 6S or GRILON™ W8361
manufactured by EMS, MXD6/MXDI a copolyamide with units from metaxylylenediamine,
adipic acic and isophthalic acid, such as GRILON™ FE458 manufactured by EMS or a multipolyamide
with monomers from hexamethylenediamine, meta-xylylenediamine, adipic acid and sebacic
acid, such as GRILON™ XE3569 manufactured by EMS. Other plasticisers and/or other
resins compatible with EVOH, as known in the art, can however be present in addition
to or alternatively to the polyamide.
[0079] Alternatively the possible complement to 100 % in said EVOH-containing core layer
can be made of one or more low molecular weight plasticisers, such as for instance
the low molecular weight diols or triols, e.g., 1,2-propanediol, butanediol, propanetriol
or pentanediol which are known to increase the stretchability of the EVOH resins.
[0080] Still alternatively the possible complement to 100 % can be made by blends of polyamides
with low molecular weight plasticisers.
[0081] In a most preferred embodiment however the core gas-barrier layer will essentially
consist of EVOH as the gas barrier properties of 100 % EVOH are much higher than those
of blended EVOH.
[0082] The thickness of said barrier layer will depend on the barrier properties desired
for the end film. More particularly its thickness will be set in order to provide
the overall multi-layer film with the desired Oxygen Transmission Rate (OTR) (evaluated
by following the method described in ASTM D-3985 and using an OX-TRAN instrument by
Mocon). For high gas barrier films an OTR lower than 100, preferably lower than 80,
and even more preferably lower than 50 cm
3/m
2.d.atm, when measured at 23 °C and 0 % of relative humidity is generally required.
Typically, when EVOH is employed as the gas-barrier material, optionally blended with
up to 20 % by weight of a polyamide, this is achieved with barrier layers 2 to 6 µm
thick. Thicker or thinner EVOH containing layers may however be employed depending
on the barrier properties required and on the particular composition of said EVOH
containing layer.
[0083] Unlike the films of the prior art, the films according to the present invention will
not contain any polyamide or polyester core layer.
[0084] They may contain additional core layers, such as "bulk" layers or "structural" layers,
i.e. layers that may be used to improve the abuse or puncture resistance of the film
or just to provide the desired thickness, "shrink" layers, i.e. layers that may be
added to improve the shrink properties of the end film, when a heat-shrinkable film
is desired, and/or "seal-assist" layers, i.e., inner layers that are directly adhered
to the second outer layer and favour the heat-sealability of the film (as described
for instance in
US-A-6,682,825 or in
US-A-6,063,462), which are polyolefin layers. Preferably these layers, if present, are positioned
between the core EVOH-containing layer and the second outer layer. Polymers particularly
suitable for any of these polyolefin layers are ethylene homo- and co-polymers, e.g.
low density polyethylene, ethylene-vinyl acetate copolymers, linear low density polyethylenes
and linear very low density polyethylenes, optionally blended with minor proportions
of other polyolefins. The thickness of these additional layers, if any, will depend
mainly on the overall thickness desired for the film.
[0085] Other layers that may be present in the multi-layer film of the invention are tie
or adhesive layers that are employed to better adhere one layer to another in the
overall structure.
[0086] In particular the films of the present invention will preferably have tie layers
directly adhered (i.e., directly adjacent) to one or both sides of the core EVOH-containing
gas-barrier layer. Tie layers may also be used, when additional core layers are present,
to better adhere said layers to the adjacent ones, e.g. to the first outer layer or
the second outer layer.
[0087] Tie layers may include polymers having grafted polar groups so that the polymer is
capable of covalently bonding to polar polymers. Useful polymers for tie layers include
ethylene-unsaturated acid copolymers, ethylene-unsaturated ester copolymers, anhydride-modified
polyolefins, and mixtures thereof. Preferred polymers for tie layers include one or
more of thermoplastic polymers such as ethylene-vinyl acetate copolymers with high
vinyl acetate content (e.g. 18- 28 wt. % or even more), ethylene-(meth)acrylic acid
copolymers, ethylene homo-polymers or co-polymers, such as LDPE, heterogeneous or
homogeneous LLDPE and VLDPE, or EVA, modified with anhydride or carboxylic acid functionalities,
blends of these resins or blends of any of the above resins with an ethylene homo-
or co-polymer, and the like known resins.
[0088] The tie layers are of a sufficient thickness to provide the adherence function, as
is known in the art. Their thickness however is generally kept as low as possible
in view of the high cost of these resins. Typically they will be from 1, preferably
2, to 10, preferably 8 µm. While layers thinner than 1 µm are generally not sufficient
to provide the desired adherence, tie layers thicker than 10 µm may well be employed
but without providing a further increase in the bond properties.
[0089] The tie layers present in the overall structure may be of a substantially similar
or of a different composition and/or thickness.
[0090] In one embodiment of the present invention the film has five layers, with the first
outer layer, the second outer layer, the EVOH-containing core gas-barrier layer, a
first tie layer directly adhering said core gas-barrier layer to the first outer layer
and a second tie layer directly adhering said core gas-barrier layer to the second
outer layer. Preferred polymers for use in said tie layers are anhydride grafted ethylene-vinyl
acetate and anhydride grafted ethylene-α-olefin copolymers that may be blended with
one or more polyolefins. Most preferred polymers are anhydride grafted ethylene-α-olefin
copolymers possibly blended with one or more polyolefins. In a most preferred embodiment
said tie layers have the same composition.
[0091] In another embodiment the film has six to eight layers with the first outer layer,
the second outer layer, the EVOH-containing core gas-barrier layer, a first tie layer
directly adhering said core gas-barrier layer to the first outer layer, a second tie
layer between said core gas-barrier layer and the second outer layer and one to three
additional core polyolefin layers positioned between the second outer layer and the
second tie layer.
[0092] In still another embodiment the film has seven to ten layers with the first outer
layer, the second outer layer, the EVOH-containing core gas-barrier layer, a first
tie layer between said core gas-barrier layer and the first outer layer, a second
tie layer between said core gas-barrier layer and the second outer layer, an additional
core polyolefin layer positioned between the first tie layer and the first outer layer,
a third tie layer directly adhering said additional core polyolefin layer to the first
outer layer and optionally one to three additional core polyolefin layers positioned
between the second outer layer and the second tie layer.
[0093] In all the film layers, not only in the outer layers, the polymer components may
contain appropriate amounts of additives normally included in such compositions. These
include slip and anti-block agents such as talc, waxes, silica, and the like, antioxidants,
fillers, pigments and dyes, cross-linking inhibitors, cross-linking enhancers, UV
absorbers, antistatic agents, anti-fog agents or compositions, and the like additives
known to those skilled in the art of packaging films.
[0094] In one particularly advantageous embodiment of the present invention, the film will
comprise at least six layers, with the first outer layer, the second outer layer,
the EVOH-containing core gas-barrier layer, a first tie layer between said core gas-barrier
layer and the first outer layer, a second tie layer between said core gas-barrier
layer and the second outer layer, and a bulk polyolefin layer positioned between the
second outer layer and the second tie layer, characterised in that the second outer
layer is very thin (few µm, e.g., about 1 to 3 µm) and comprises slip and anti-blocking
agents and the bulk layer which is directly adhered thereto, is a thicker layer containing
the anti-fog additives. In a preferred embodiment said bulk layer comprises the same
polymer or polymer cmposition of the adjacent second outer layer. By the time the
film is used in packaging applications these additives, which are known to migrate
within the polyolefin layers, will be present on the outer surface of the second outer
layer.
[0095] Preferably, the film of the present invention has an overall thickness of from about
10 to 80 µm, more preferably, from 12 to 70 µm, and, still more preferably, from 14
to 60 µm.
[0096] The film according to the present invention can be obtained by melt extruding the
polymers or polymer blends used for each layer through a flat die, cooling quickly
the multi-layer sheet exiting from the extrusion die by means of a chill roll, optionally
irradiating the cast sheet thus obtained to get cross-linking, reheating this flat
tape to the suitably selected orientation temperature, and biaxially stretching the
heated tape at a stretching ratio of at least 2:1 in each direction, by a tenter apparatus,
optionally stabilizing the obtained bi-axially oriented film by an annealing or a
heat-setting step and finally cooling the thus obtained bi-axially oriented, multi-layer
film.
[0097] The biaxial stretching will be carried out simultaneously as it has been found that
it is possible in this way to reach much higher stretching ratios, even when the core
EVOH-containing layer does not comprise plasticizers, and obtain films with a higher
modulus.
[0098] In particular it has been found that using the simultaneous flat orientation technique
in connection with a multi-layer tape with a first outer layer comprising a polyester
or a copolyester, a second outer layer comprising an ethylene- or propylene- homo-
or copolymer, a core layer comprising an ethylene-vinyl alcohol copolymer, and no
core polyamide or polyester layers, it is possible to easily reach stretching ratios
of 5:1 in each direction even when the core gas-barrier layer is 100 % EVOH and it
is expected that also higher stretching ratios, such as for instance 5.5:1, 6:1, or
6.5:1, could be applied, at least in one direction, possibly by suitably adjusting
the stretching conditions and/or the composition of the core EVOH-containing layer.
[0099] The oriented films thus obtained, whether heat-shrinkable or heat-set, are characterized
by a modulus higher than 6,000 kg/cm
2 in at least one direction.
[0100] Preferred films of the present invention have a modulus higher than 6,500 kg/cm
2 in at least one direction, and more preferably higher than 7,000 kg/cm
2 in at least one direction. Even more preferred films of the present invention have
a modulus higher than 6,000 kg/cm
2 in both directions.
[0101] Using the simultaneous tenter frame stretching technique it is also possible to obtain
a bi-axially oriented heat-shrinkable film with a maximum shrink tension in the transverse
direction, in the temperature range of from 20 to 180°C, of less than 5 kg/cm
2. Such a low shrink tension value in the transverse direction can be obtained also
with heat-shrinkable films showing a high free shrink at 120°C, e.g., films with a
total free shrink at 120 °C of 40 %, 50 %, 60 %, or even more.
[0102] A second object of the present invention is therefore a process for the manufacture
of a bi-axially oriented, thermoplastic, multi-layer film comprising a first outer
layer comprising a polyester or a copolyester, a second outer layer comprising an
ethylene-or propylene homo- or co-polymer, a core layer comprising an ethylene-vinyl
alcohol copolymer, and no polyamide or polyester core layers, which process comprises
co-extrusion of the film resins through a flat die and bi-axial orientation of the
obtained cast sheet, by means of a tenter frame, simultaneously in the two perpendicular
directions at an orientation ratio in the longitudinal direction higher than 2:1,
preferably higher than 3:1 and at an orientation ratio in the cross-wise direction
higher than 2:1, preferably higher than 3:1.
[0103] The process according to the present invention involves feeding the extruders with
the solid polymer or polymer blend beads for the various layers, melting the polymer
beads in the extruders and then forward the molten resins of the layers into a flat
extrusion die where they are combined to give the desired sequence. The obtained tape,
that is preferably from 0.1 mm to 2 mm thick, is then cooled, either by means of a
chill roll, typically with the aid of an air knife or an electrostatic pinning system
to keep the sheet in contact with the chill roll, or by using a liquid-knife as described
in
WO-A-95/26867 where a continuous and substantially uniform layer of water or of any other cooling
liquid flows onto the surface of the sheet that does not contact the chill roll. Any
other known means for cooling the cast web can however be employed.
[0104] The cooled sheet is then optionally fed through an irradiation unit, typically comprising
an irradiation vault surrounded by a shielding. The flat sheet may in fact be irradiated
with high energy electrons (i.e., ionizing radiation) from an iron core transformer
accelerator. Irradiation is carried out to induce cross-linking. The flat sheet is
preferably guided through the irradiation vault on rolls. It is thus possible by suitably
combining the number of rolls and the path of the traveling web within the irradiation
unit to get more than one exposure of the sheet to the ionizing radiation. In one
embodiment, the sheet is irradiated to a level of from about 10 to about 200 kGy,
preferably of from about 15 to about 150 kGy, and more preferably of from about 20
to about 120 kGy, wherein the most preferred amount of radiation is dependent upon
the polymers employed and the film end use. While irradiation is preferably carried
out on the extruded cast sheet just before orientation, as described above, it could
also be carried out, alternatively or additionally, during or after orientation.
[0105] The optionally irradiated tape is then fed to the pre-heating zone of a simultaneous
tenter apparatus, with or without a prior passage through an IR heated oven. The temperature
of the oven in said pre-heating zone, the length thereof and the time spent by the
traveling web in said zone (i.e. the web speed) can suitably be varied in order to
bring the sheet up to the desired temperature for bi-axial orientation. In a preferred
embodiment the orientation temperature is comprised between 90°C and 140°C and the
temperature of the pre-heating zone is kept between 90°C and 150°C. In said pre-heating
zone the sheet is clipped but it is not yet stretched. Thereafter, the resulting hot,
optionally irradiated, and clipped sheet is directed to the stretching zone of the
simultaneous tenter. Any simultaneous stretching means can be used in said zone. Preferably
however the clips are propelled throughout the opposed loops of the tenter frame by
means of a linear synchronous motor. A suitable line for simultaneous stretching with
linear motor technology has been designed by Brückner GmbH and advertised as LISIM®
line. An alternative line for simultaneous stretching of the extruded flat tape is
the DMT line, based on a pantograph, equipped with two separated monorails on each
side of the orientation unit. The configuration of the tenter can be varied depending
on the stretching ratios desired. The stretching ratios that are applied in the process
according to the present invention are generally comprised between 2:1 and 5:1 for
MD stretching and between 2:1 and 5:1 for TD stretching. Preferably however stretching
ratios higher than 2.5:1 in both directions are applied, wherein stretching ratios
higher than 3:1 in both directions are more preferred. The temperature in the stretching
zone is kept close to the selected orientation temperature. The stretched film is
then transferred in a zone that, depending on whether a heat-shrinkable or non heat-shrinkablefilm
is desired, may be a relaxation/annealing or heat-setting zone, heated to a temperature
of 70-100 °C, or 130-170°C respectively. Following said annealing or heat-setting
step the film is transferred to a cooling zone where generally air, either cooled
or kept at the ambient temperature, is employed to cool down the film. The temperature
of said cooling zone is therefore typically comprised between 20 and 40 °C. At the
end of the line, the edges of the film, that were grasped by the clips and have not
been oriented, are trimmed off and the obtained bi-axially oriented, heat-shrinkable
or heat-set film is then wound up, with or without prior slitting of the film web
to the suitable width.
[0106] To allow recycling of the trimmed edges, or at least of part thereof, a multi-manifold
die may preferably be employed in the co-extrusion so that the edges of the extruded
tape that will be grasped by the clips are of a single polymer or polymer composition,
typically, in the present process, the polymer(s) of the first outer layer.
[0107] The bi-axially oriented film of the present invention, when heat-shrinkable, may
have a total % free shrink (% shrink in MD + % shrink in TD), at 120 °C, of from 20
to 140 %, preferably from 30 to 130 %, more preferably from 40 to 120 %, and still
more preferably from 50 to 110 %.
[0108] As indicated above the bi-axially oriented heat-shrinkable films obtained by the
process according to the present invention, are also characterised by a maximum shrink
tension in at least the transverse direction, in the temperature range of from 20
to 180 °C, of less than 5 kg/cm
2, preferably less than 3 kg/cm
2, and more preferably less than 1 kg/cm
2.
[0109] The biaxially oriented films of the present invention, when heat-set, will have a
free shrink, at 120 °C, lower than 10 %, preferably lower than 5 %, more preferably
lower than 3 %, and even more preferably lower than 2 %, in each direction.
[0110] The films thus obtained have a thickness variation of less than 10 percent, preferably
less than 8 percent, and more preferably less than 5 percent.
[0111] The thus obtained films may then be subjected to a corona discharge treatment to
improve the print receptivity characteristics of the film surface. As used herein,
the phrases "corona treatment" and "corona discharge treatment" refer to subjecting
the outer surfaces of the film to a corona discharge treatment, i.e., the ionization
of a gas such as air in close proximity to a film surface, the ionization initiated
by a high voltage passed through a nearby electrode, and causing oxidation and other
changes to the film surface, such as surface roughness. Corona treatment of polymeric
materials is disclosed in e.g.
US-A-4, 120,716.
[0112] The thus obtained films may also be coated on the surface of the second outer layer
with e.g. an antifog composition, with or without a binder to incorporate the antifog
additive into the film; a liquid smoke; an aroma transfer composition; an antibacterial
or anti-mould composition; etc. as known in the field.
[0113] The present invention is further illustrated by the following examples, which are
provided for the purpose of representation, and are not to be construed as limiting
the scope of the invention.
Example 1
[0114] A five-layer, heat-shrinkable film with the following layer arrangement (B)/(D)/(A)/(D)/(C),
a total thickness of 25 µm, and a thickness ratio of 4/1/1/1/1.3 is produced by the
general process described above. In particular, the temperature of the chill roll
is kept at 15-25 °C and the extruded sheet is pinned to the chill roll by means of
an air knife. The thickness of the cast extruded sheet before orientation is about
0.4 mm and the linear speed of the quenched sheet is about 8 m/min. The sheet is not
irradiated. The temperature in the pre-heating zone is kept between about 120 and
about 130 °C. The stretching ratios applied are 4:1 in MD and 4:1 in TD and the temperature
in the stretching zone is maintained between about 110 and about 120 °C. The annealing
step is carried out at about 80-85 °C and the cooling step at about 30-35 °C. After
cooling, the film edges are trimmed off and the film is wound onto a roll at a speed
of about 36 m/min.
[0115] The resins employed for the various layers were as follows:
- (A) EVOH-1 (= ethylene-vinyl alcohol copolymer containing 44 mole % of ethylene (EVAL™
E151B from Marubeni));
- (B) EAO-1 (= a blend of 50 wt. % of a heterogeneous ethylene-octene copolymer with
a density of 0.920 g/cm3 and a melt index of 1.0 g/10 min (Dowlex™ 2045 by Dow); 25 wt. % of a heterogeneous
ethylene-octene copolymer with a density of 0.935 g/cm3 and a melt index of 2.6 g/10 min (Dowlex™ SC 2108 by Dow); 15 wt. % of a homogeneous
ethylene-octene copolymer with a density of 0.902 g/cm3 and a melt index of 1.0 g/10 min (Affinity™ PL1850 by Dow); and 10 wt. % of a master-batch
based on ethylene-vinyl acetate copolymer (3.5 % of vinyl acetate content) containing
slip (3 wt. %) and anti-block (0.9 wt. %) agents);
- (C) PET-1 (= PETG with Tg 81 °C (Eastar 6763 by Voridian));
- (D) Tie- 1 (= homogeneous ethylene-α-olefin copolymer (Tafmer™ like) with d = 0.906
g/cm3 and MFI = 1.5 g/10', modified with maleic anhydride (m.p. 116°C) (ADMER™ AT1094E
by Mitsui)).
[0116] The modulus of the obtained film was 6,400 kg/cm
2 in LD and 7,000 kg/cm
2 in TD.
[0117] The free shrink at 120 °C was 43 % in LD and 50 % in TD.
[0118] The shrink force was evaluated by the method described hereinbelow in the temperature
range of from 20 to 180 °C and the maximum shrink tension thus determined was 0.14
kg/cm
2 in TD (at 113 °C) and 0.21 kg/cm
2 in LD (at 110 °C): specimens of the films (2.54 cm x 14.0 cm) were cut in the longitudinal
and transverse directions and clamped between two jaws, one of which was connected
to a load cell. The two jaws kept the specimen in the center of a channel into which
an impeller blowed heated air and three thermocouples measured the temperature. The
signal supplied by the thermocouples was amplified and sent to an output connected
to the "X" axis of an X/Y recorder. The signal supplied by the load cell was also
amplified and sent to the "Y" axis of the X/Y recorder. The impeller started blowing
hot air and the force released by the sample was recorded in grams. As the temperature
increased, the measured profile of the shrink force versus the temperature was drawn
on the X/Y recorder. When the temperature of 180 °C was reached, the heater was turned
off, the specimen temperature gradually reduced and the profile of the shrink force
under negative temperature gradients (cooling) was recorded.
[0119] The instrument produced a curve of the shrink force (g) versus temperature (°C);
dividing the value by the specimen width, shrink force in kg/cm was obtained and further
dividing by the specimen thickness the shrink tension, in kg/cm
2, was obtained.
Example 2
[0120] A five-layer, heat-shrinkable film with essentially the same layer arrangement as
in Example 1 but with PET-2 (= PET 18696 with I.V. 0.71 by Voridian) replacing the
PET-1 in layer (C), and with a thickness ratio of 5/1/1/1/1.5 is produced by the same
process described in Example 1 with the only difference that the stretching ratio
was 3:1 in the longitudinal direction and 3.5:1 in the transverse direction.
[0121] A film with a thickness of 25 µm was obtained characterized by a modulus of 7,000
kg/cm
2 in LD and 9,000 kg/cm
2 in TD.
[0122] The film had a free shrink of 15 % in LD and 55 % in TD at 120 °C and a shrink tension
of 0 kg/cm
2 in TD and 1.20 kg/cm
2 in LD (at 105 °C)
Example 3
[0123] A five-layer, heat-shrinkable film with the same layer arrangement and thickness
ratio as in Example 1 is produced by the same process there described with the only
difference that the cast sheet is irradiated before orientation to 45 kGray by means
of a scan beam unit operated at 500 kVolt and the sheet is passed twice under the
irradiation window to provide for a uniform cross-linking.
Example 4
[0124] The process of Example 1 has been repeated with the only difference that instead
of annealing at a temperature of 85-90°C, the bi-axially oriented film is heat-set
at a temperature of 110-120 °C by reducing the line speed by 20 % and allowing the
stretching clips to converge by 20 %.
[0125] The obtained film showed a total % free shrink (% free shrink in MD + % free shrink
in TD) at 120 °C lower than 5.
Example 5
[0126] The process of Example 2 has been repeated with the only difference that instead
of annealing at a temperature of 85-90°C, the bi-axially oriented film was heat-set
at a temperature of 110-120 °C by reducing the line speed by 20 % and allowing the
stretching clips to converge by 20 %.
[0127] The obtained film showed a total % free shrink at 120 °C lower than 5.
Examples 6-10
[0128] The five layer heat-shrinkable films of Examples 6 to 10, having the following layer
arrangement (B)/(D)/(A)/(D)/(C), have been prepared by substantially the same general
process described in Example 1, with the following modifications : for melt casting
an electrostatic pinning system (tension 12 kVolt and current 2 mA) was used instead
of the air knife; the temperatures used in the pre-heating/stretching /annealing zones
were 100-110/95-100/95-100 °C respectively; and 5 % relaxation in MD was applied in
the annealing zone.
[0129] The resins used for the different layers, the thickness of each layer, as well as
the stretching ratios (SR) applied and the shrink values at 120°C for some representative
structures, are reported in following Table 1
Table 1
Ex. No. |
(B) (µm) |
(D) (µm) |
(A) (µm) |
(C) (µm) |
SR |
MD/TD % shrink at 120°C |
6 |
EAO-2 (18) |
Tie-1 (3)* |
EVOH-1 (3) |
PET-3 (8) |
4x4.5 |
25/36 |
7 |
EAO-2 (18) |
Tie-1 (3)* |
EVOH-1 (3) |
PET-4 (8) |
4x4 |
22/14 |
8 |
EAO-3 (7) |
Tie-1 (3)* |
EVOH-1 (3) |
PET-5 (12) |
3.3x3.5 |
|
9 |
EAO-3 (7) |
Tie-1 (3)* |
EVOH-1 (3) |
PET-5 (12) |
3.3x3.8 |
|
10 |
EAO-4 (9) |
Tie-2 (3)* |
EVOH-1 (3) |
PET-5 (10) |
3.3x3.8 |
|
*Both tie layers had the same thickness |
[0130] EAO-2 = blend of 90 wt. % of a homogeneous ethylene-octene copolymer with density
of 0.910 g/cm
3 and melt index of 3.5 g/10 min (Affinity™ PL1845 by Dow) and 10 wt. % of a master-batch
based on ethylene-vinyl acetate copolymer (3.5 % of vinyl acetate content) containing
slip (3 wt. %) and anti-block (0.9 wt. %) agents;
[0131] EAO-3 = blend of 90 wt. % of a homogeneous ethylene-octene copolymer with density
of 0.910 g/cm
3 and melt index of 3.5 g/10 min (Affinity™ PL1845 by Dow) and 10 wt. % of a master-batch
based on ethylene-vinyl acetate copolymer (3.5 % of vinyl acetate content) containing
slip (3 wt. %) and anti-block (1.5 wt. %) agents;
[0132] EAO-4 = blend of 50 wt. % of a homogeneous ethylene-octene copolymer with density
of 0.910 g/cm
3 and melt index of 3.5 g/10 min (Affinity™ PL1845 by Dow) and 50 wt. % of a master-batch
based on heterogeneous ethylene-octene copolymer with a density of 0.920 g/cm
3 and a melt index of 1.0 g/10 min (Dowlex™ 2045 by Dow) containing antiblock (0.7
wt. %) agents, 4 wt. % of polyethoxylated (C
12 -C
14) alcohols, and 2 wt. % glycerol mono- and di-oleate;
[0133] Tie 2 = ethylene-α-olefin copolymer with d = 0.915 g/cm
3 and MFI = 4.5 g/10', modified with maleic anhydride (ADMER™ NF911 by Mitsui);
[0134] PET-3 = a blend of 97 wt. % PETG with Tg 81°C (Eastar 6763 by Voridian) and 3 wt.
% of a master-batch based on PET containing slip and antiblock agents (Sukano GDC
S503);
[0135] PET-4 = a blend of 97 wt. % PET with I.V. 0.71 (PET 18696 by Voridian) and 3 wt.
% of a master-batch based on PET containing slip and antiblock agents (Sukano GDC
S503);
[0136] PET-5 = a blend of 95 wt. % PET with I.V. 0.71 (PET 18696 by Voridian) and 5 wt.
% of a master-batch based on PET containing slip and antiblock agents (Sukano GDC
S503);
Example 11
[0137] A five-layer, heat-shrinkable film with the same layer arrangement as in Example
7 but with EPC-1 (a blend of 90 wt. % of a propylene-ethylene copolymer with 3.4 %
of ethylene units, and m.p. 134 °C (Eltex PKS 400 by Solvay) and 10 wt. % of a masterbatch
based on polypropylene containing slip (3 wt. %) and anti-blocking (0.5 wt. %) agents)
to replace EAO-2 in layer (B), has been prepared by following essentially the same
process of examples 6-10 but using stretching ratios of 3.8 X 4.2. The film showed
a % free shrink at 120 °C of 30 (MD) and 23 (TD).
Examples 12-14
[0138] The processes of Examples 6, 7, and 11 have been repeated with the only difference
that instead of being annealed, the bi-axially oriented films have been heat-set at
a temperature of 130-140 °C by reducing the line speed by 20 % and allowing the stretching
clips to converge by 20 %.
[0139] The obtained films showed a free shrink at 120 °C ≤ 2 % in each direction.
Example 15
[0140] A heat-set, biaxially oriented, five-layer film with the following structure
EAO-3 (13 µm) /Tie-1 (3 µm) /EVOH-1 (3 µm) /Tie-1 (3 µm) /PET-5 (13 µm)
has been prepared by the general process of example 9 but replacing the annealing
step with a heat-setting step carried out at an average temperature of about 160°C.
Examples 16 and 17
[0141] The films of these examples have been prepared as described in Example 15 but replacing
PET-5 with PET-6 (example 16) and PET-7 (example 17), respectively, wherein
PET-6 = a blend of 92 wt. % PET with I.V. 0.71 (PET 18696 by Voridian), 5 wt. % of
a master-batch based on PET containing slip and antiblock agents (Sukano GDC S503),
and 3 wt. % of a PETG-based masterbatch containing talc as the nucleating agent;
and
PET-7 = a blend of 92 wt. % PET with I.V. 0.71 (PET 18696 by Voridian), 5 wt. % of
a master-batch based on PET containing slip and antiblock agents (Sukano GDC S503),
and 3 wt. % of a terpolymer propylene-butylene-ethylene with m.p. 135 °C (Adsyl 5C37F
by Basell) as the nucleating agent.
Examples 18-23
[0142] Five-layer, heat-set films, having the following layer arrangement
(B) (11 µm) /(D) (3 µm) /(A) (3 µm) /(D) (3 µm) /(C) (15 µm)
wherein the resins employed for each layer are reported in Table 2 below, have been
prepared by the process of Example 15 but applying stretching ratios of 3.3 x 3.5.
Table 2
Ex. No. |
(B) |
(D) |
(A) |
(C) |
18 |
EAO-3 |
Tie-1 |
EVOH-1 |
PET-4 |
19 |
EAO-3 |
Tie-2 |
EVOH-1 |
PET-4 |
20 |
EAO-3 |
Tie-1 |
EVOH-1 |
PET-6 |
21 |
EAO-3 |
Tie-1 |
EVOH-1 |
PET-8 |
22 |
EAO-3 |
Tie-1 |
EVOH-1 |
PET-9 |
23 |
EAO-3 |
Tie-1 |
EVOH-1 |
PET-10 |
[0143] PET-8 = a blend of 95 wt. % PET with I.V. 0.80 (PET 9921W by Voridian) and 5 wt.
% of a master-batch based on PET containing slip and antiblock agents (Sukano GDC
S503);
[0144] PET-9 = a blend of 92 wt. % PET with I.V. 0.80 (PET 9921W by Voridian), 5 wt. % of
a master-batch based on PET containing slip and antiblock agents (Sukano GDC S503),
and 3 wt. % of a PETG-based masterbatch containing talc as the nucleating agent;
[0145] PET-10 = a blend of 92 wt. % of PET with I.V. 0.9 (PET 12822 by Voridian), 5 wt.
% of a master-batch based on PET containing slip and antiblock agents (Sukano GDC
S503), and 3 wt. % of a PETG-based masterbatch containing talc as the nucleating agent.
Examples 24-25
[0146] The following heat-set structures have been prepared by the same general process
of Example 15 but applying stretching ratios of 3.5 x 4.2 :
Ex. 24 EAO-2 (16 µm) /Tie-1 (3.5 µm) /EVOH-1 (3 µm) /Tie-1 (3.5 µm) /PET-4 (14 µm)
Ex. 25 EAO-2 (13 µm) /Tie-1 (3.5 µm) /EVOH-2 (3 µm) /Tie-1 (3.5 µm) /PET-4 (14 µm)
wherein
EVOH-2 = ethylene-vinyl alcohol copolymer containing 32 mole % of ethylene (EVAL™
F101B from Marubeni));
[0147] The heat-set films of examples 15 to 25 have a % free shrink at 120 °C which is ≤
1 in each direction.
Example 26
[0148] The following heat-set film has been prepared by the same general process of Example
15 but applying stretching ratios of 3.3 x 4.0
EAO-2 (24 µm) /Tie-1 (5 µm) /EVOH-1 (5 µm) /Tie-1 (5 µm) /PET-4 (21 µm)
Example 27
[0149] By following substantially the same process described in Example 15 it is possible
to prepare a film differing from that of Example 15 for the second outer layer (B)
where a blend of 40 wt. % of a propylene-butylene-ethylene terpolymer with m.p. 135
°C (Adsyl 5C37F by Basell) and 60 wt. % of a masterbatch based on an ethylene-α-olefin
plastomer with density of 0.902 g/cm
3 and m.p. 99 °C (Affinity PL1880 by Dow) containining 4 wt. % of polyethoxylated (C
12 -C
14) alcohols and 2 wt. % glycerol mono- and di-oleate (EAO-5) replaces EAO-3.
Examples 28 and 29
[0150] By following subtantially the same process described in Example 15 it is possible
to prepare six layer films with the following arrangement of layers (B)/(E)/(D)/(A)/(D)/(C)
and thickness ratio of 1/6/1.5/1.5/1.5/6 wherein the composition of layers (A), (D),
and (C) is as in Example 15, and
in Example 28 layer (B) is a propylene-butylene-ethylene terpolymer with m.p. 135
°C (Adsyl 5C37F by Basell) containing 3 wt. % slip and 1 wt. % antiblocking agents
and layer (E) is EAO-5 and,
in Example 29 layer (B) is EAO-2 and layer (E) is a blend of 50 wt. % of a homogeneous
ethylene-octene copolymer with density of 0.910 g/cm
3 and melt index of 3.5 g/10 min (Affnity™ PL1845 by Dow) and 50 wt. % of a master-batch
based on heterogeneous ethylene-octene copolymer with a density of 0.920 g/cm
3 and melt index of 1.0 g/10 min (Dowlex™ 2045 by Dow) containing 4 wt. % of polyethoxylated
(C
12-C
14) alcohols, and 2 wt. % glycerol mono- and di-oleate (EAO-6).
[0151] The films obtained according to the present invention can be used in the packaging
of food and non food, oxygen-sensible, products as known in the art. To this purpose
they can be used as such in the form of a film or laminate and either wrapped up around
the product or employed as a lid for any suitable container such as a tray, or they
may be first converted into flexible containers, such as bags or pouches, by conventional
techniques well known to the person skilled in the art. They can also be coupled or
laminated to other films or sheets to obtain a packaging material of improved performance.
[0152] In a most preferred embodiment the biaxially oriented non heat-shrinkable films of
the present invention can conveniently be employed in all those processes that actually
use sheets of biaxially oriented polyester (BO-PET) glue-laminated to a heat-sealable
barrier film. While the performance of the films of the present invention in these
packaging processes is at least comparable to that obtained with the conventional
laminates because of the remarkable stiffness of the films of the present invention,
the process for the manufacture thereof is much easier and much more convenient as
any lamination step may be avoided, as well as the use of any glue and solvent involved
therein.
[0153] Although the present invention has been described in connection with the preferred
embodiments, it is to be understood that modifications and variations may be utilized
without departing from the principles and scope of the invention, as those skilled
in the art will readily understand. Accordingly, such modifications may be practiced
within the scope of the following claims.
1. Mehrschichtige, biaxial orientierte, thermoplastische Folie, umfassend eine erste
äußere, einen Polyester oder einen Copolyester umfassende Schicht, eine zweite äußere,
ein Ethylen- oder Propylen-Homopolymer oder -Copolymer umfassende Schicht, eine ein
Ethylen-Vinylalkohol-Copolymer umfassende Kernschicht und keinen Kern bildende Polyamid-
oder Polyesterschichten, wobei die Folie einen Modul (ausgewertet nach ASTM D882)
von höher als 6.000 kg/cm2 in mindestens einer Richtung aufweist.
2. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach Anspruch 1, bei
der die zweite äußere Schicht ein Ethylen-Homo- oder -Copolymer umfasst.
3. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach Anspruch 1 oder
2, gekennzeichnet durch einen Modul von höher als 7.000 kg/cm2 in mindestens einer Richtung.
4. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 3, der wärmeschrumpfbar ist und eine gesamte freie Schrumpfung bei
120 °C, von zwischen 20 und 140 Prozent aufweist (wobei die Schrumpfung in jeder Richtung
nach ASTM D2732 ausgewertet wird).
5. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach Anspruch 4, gekennzeichnet durch eine maximale Schrumpfspannung in der Querrichtung im Temperaturbereich von 20 bis
180 °C, von weniger als 5 kg/cm2 (ausgewertet nach der Verfahrensweise gemäß den Abschnitten
00125 und 00126 der Beschreibung).
6. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 3, die nicht wärmeschrumpfbar und wärmehärtbar ist, gekennzeichnet durch eine freie Schrumpfung bei 120 °C, die in jeder Richtung ≤ 10% beträgt.
7. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach Anspruch 6, gekennzeichnet durch eine freie Schrumpfung, die bei 120 °C in jeder Richtung ≤3% beträgt.
8. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 7, wobei der Polyester oder Copolyester der ersten äußeren Schicht
ein einen aromatischen Ring enthaltendes Polymer ist.
9. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach Anspruch 2, wobei
die Ethylen-Homo- und -Copolymere der zweiten äußeren Schicht ausgewählt sind aus
der Gruppe bestehend aus Polyethylen-Homopolymeren, heterogenen oder homogenen Ethylen-α-Olefin-Copolymeren,
EthylenVinylacetat-Copolymeren, Ethylen-(C1-C4)Alkylacrylat- oder -Methylacrylat-Copolymeren,
Ethylen-Acrylsäure-Copolymeren und Mischungen davon in beliebigen Verhältnissen.
10. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 9, aufweisend fünf Schichten, mit einer ersten äußeren, einen Polyester
oder einen Copolyester umfassenden Schicht, einer zweiten äußeren, ein Ethylen- oder
Propylen-Homo- oder -Copolymer umfassenden Schicht, einer ein Ethylen-Vinylalkohol-Copolymer
umfassenden Kernschicht, einer ersten Bindeschicht, die die Kern-Gasbarriereschicht
direkt an die erste äußere Schicht bindet, und einer zweiten Bindeschicht, die die
Kern-Gasbarriereschicht direkt an die zweite äußere Schicht bindet.
11. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 9, aufweisend sechs bis acht Schichten, mit einer ersten äußeren,
einen Polyester oder Copolyester umfassenden Schicht, einer zweiten äußeren, ein Ethylen-
oder Propylen-Homo- oder -Copolymer umfassenden Schicht, einer ein Ethylen-Vinylalkohol-Copolymer
umfassenden Kernschicht, einer ersten Bindeschicht, die die EVOH enthaltende Kernschicht
direkt an die erste äußere Schicht bindet, einer zweiten Bindeschicht, die die EVOH
enthaltende Kernschicht direkt an die zweite äußere Schicht bindet und eine bis drei
zusätzliche Polyolefin-Kernschichten, die zwischen der zweiten äußeren Schicht und
der zweiten Bindeschicht angeordnet sind.
12. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 9, aufweisend sieben bis zehn Schichten, mit einer ersten äußeren,
einen Polyester oder einen Copolyester umfassenden Schicht, einer zweiten äußeren,
ein Ethylen- oder Propylen-Homo- oder - Copolymer umfassenden Schicht, einer ein Ethylen-Vinylalkohol-Copolymer
umfassenden Kernschicht, einer ersten Bindeschicht, zwischen der EVOH enthaltenden
Kernschicht und der ersten äußeren Schicht, einer zweiten Bindeschicht, zwischen der
EVOH enthaltenden Kernschicht und der zweiten äußeren Schicht, eine dritte Bindeschicht,
die die zusätzliche Polyolefin-Kernschicht direkt an die erste äußere Schicht binden,
und fakultativ eine bis drei zusätzliche Pololefin-Kernschichten, die zwischen der
zweiten äußeren Schicht und der zweiten Bindeschicht angeordnet sind.
13. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 12, umfassend beschlaghemmende Mittel oder Zusammensetzungen in der
zweiten äußeren Schicht oder / und in einer Polyolefin-Kernschicht, die möglicherweise
zwischen der zweiten äußeren Schicht und der EVOH enthaltenden Schicht angeordnet
ist.
14. Die mehrschichtige, biaxial orientierte, thermoplastische Folie nach einem der vorhergehenden
Ansprüche 1 bis 13, die bis zu einem Niveau von 10 bis 200 kGy bestrahlt ist.
15. Verfahren zur Herstellung einer biaxial orientierten, thermoplastischen Folie, umfassend
eine erste äußere, einen Polyester oder einen Copolyester umfassende Schicht, eine
zweite äußere, ein Ehtylen- oder Propylen-Homo- oder -Copolymer umfassende Schicht,
eine ein Ethylen-Vinylalkohol-Copolymer umfassende Kernschicht und keine Polyamid-
oder Polyester-Kernschichten, wobei die Folie einen Modul von höher als 6.000 kg/cm2
in mindestens einer Richtung aufweist, wobei das Verfahren das Coextrudieren der Folienharze
durch eine flache Düse und biaxial die erhaltene Folie gleichzeitig orientierend in
den beiden senkrechten Richtungen bei einem Orientierungsverhältnis in der Längsrichtung
von größer als 2:1 und bei einem Orientierungsverhältnis in der Querrichtung von größer
als 2:1, mittels eines Spannrahmens, aufweist, wobei dem Verfahren ein Glüh- oder
Wärmehärtungsschritt fakultativ nachfolgen kann.
16. Das Verfahren nach Anspruch 15, wobei die Orientierungsverhältnisse in der Längsrichtung
und der Querrichtung größer sind als 3:1.